Materials Letters 284 (2021) 129018

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Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

Fabrication of high-porosity open-cell aluminum foam via

high-temperature deformation of CaCl2 space-holders
Tan Wan a, Yuan Liu a,b,⇑, Canxu Zhou a,b, Xiang Ding a,b, Xiang Chen a,b, Yanxiang Li a,b
a
School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China
b
Key Laboratory for Advanced Materials Processing Technology (Ministry of Education), Beijing 100084, China

a r t i c l e i n f o a b s t r a c t

Article history: In this study, we found that porous CaCl2 granules can be easily deformed under certain pressure and
Received 8 September 2020 temperature conditions. Based on this finding, a new infiltration process that employs CaCl2 granules
Received in revised form 27 October 2020 as space-holders was developed to prepare aluminum (Al) foam with high porosity. In this process, por-
Accepted 8 November 2020
ous CaCl2 granule preforms were first subjected to hot-pressing deformation, which provided two bene-
Available online 12 November 2020
fits: 1) the density of the preform was increased, thereby increasing the porosity of the final prepared
open-cell Al foam (over 80%) and 2) the contact surface of the neighboring CaCl2 granules was increased.
Keywords:
After hot-pressing, the sizes of the dissolution and removal channels of CaCl2 increased. Consequently,
Porous materials
Space-holder process
the space-holder particles could be completely removed, which is just the most difficult bottleneck prob-
Cast lem in the traditional infiltration process applying salt particles as space-holders in which the salt
CaCl2 preform removal is not enough and the porosity is lower than 65%.
Hot-pressing deformation Ó 2020 Elsevier B.V. All rights reserved.

1. Introduction forms with various densities using two preform processing

Open-cell metal foams attracted widespread attention owing to
their multifunctional and integrated performance, with character-
istics such as their lightweight, high specific stiffness, good energy
and sound absorption, and excellent heat dissipation capacity [1].
Among the techniques currently employed to manufacture the
foam, the space-holder process is one of the most convenient
methods adopted to produce various open-cell metal foams owing
to its experimental simplicity and capacity to fabricate metal
foams with homogenous controllable pore structures. This tech-
nique can generally be divided into two fundamental categories
of powder metallurgy [2] and infiltration casting [3], of which
the latter is cost-efficient and perfect for liquid aluminum with
good fluidity.
Despite the abovementioned advantages, low porosity (usu-
ally < 65%) and difficulty of space-holder removal often arise in
infiltration casting owing to the low packing density. Generally,
Water-soluble space-holders are the most popular for their energy
saving and environmental protection, including inorganic salts
(NaCl, CaCl2, MgSO4, and etc.) and organic particles (carbamide,
saccharose, and etc.) [1,4]. Goodall et al. [5] prepared NaCl pre-
approaches: sintering NaCl granules at high temperature and cold
isostatic pressing. These approaches are effective for controlling
preform density; however, they are only practical when using
microscale NaCl granules and for small-size preforms [6]. The poor
compressibility of inorganic salts limits the degree of control over
preform density [7,8]. To solve this problem, Kan et al. [8] pro-
duced soft ceramic balls by mixing Al2O3 powders, water, polyvinyl
alcohol, and small amounts of bentonite and cellulose. Goodall and
Mortensen [9] prepared compressible space-holders from a paste
comprising a mixture of salt, flour, and water. These two proce-
dures are useful for adjusting the space-holder packing density
over a wide range, but the fabrication of space-holders is compli-
cated and time- consuming.
To solve these shortcomings, it is desirable to improve the com-
pressibility of space-holders in a simple and effective way. There-
fore, high-temperature deformation of porous CaCl2 granules
assisted by hot-pressing is proposed to improve foam porosity
and reduce the difficulty of space-holder removal.
2. Materials and methods

Spherical CaCl2 granules (provided by Zhejiang Dacheng Cal-

⇑ Corresponding author at: School of Materials Science and Engineering, Tsinghua cium Industry Co., Ltd., purity  98%) with a diameter of 4.5 mm
University, Beijing 100084, China. and 6061-T6 Al alloy were selected as starting materials. A sche-
E-mail address: yuanliu@tsinghua.edu.cn (Y. Liu). matic of the open-cell aluminum foam manufacturing process is

https://doi.org/10.1016/j.matlet.2020.129018
0167-577X/Ó 2020 Elsevier B.V. All rights reserved.
T. Wan, Y. Liu, C. Zhou et al.
shown in Fig. 1. Two types of CaCl2 preforms were prepared by hot-
pressing for different holding times. CaCl2 granules with a total
mass of 50 g were hot-pressed in a mould of 55 mm in inner diam-
eter and 80 mm in height at 60 kPa and 700 °C for 5 and 30 min
once reaching the furnace temperature. Another preform, manu-
factured without hot-pressing and with no holding time, was used
as a reference. Accordingly, CaCl2 preforms (labeled A, B, and C for
0, 5, and 30 min holding times, respectively) with various packing
densities were obtained. These preforms were later infiltrated with
molten Al at 700 °C and 0.1 MPa. After solidification, Al-CaCl2 com-
posites were machined by engine lathe to remove the aluminum
skin. The CaCl2 preforms were subsequently leached out in flowing
water at room temperature for 1 h and the final foams were dried
to a constant weight (60 °C for 2 h) to obtain Al foams (labeled as A,
B, and C, having been made from preforms A, B, and C, respectively)
of different porosities. In order to improve the reliability of the
experiment, a sum of three preforms were produced and infiltrated
by liquid aluminum for each condition of preform processing.
The structures of the CaCl2 preforms were observed by Micro CT
(Quantum GX micro CT, PerkinElmer, USA) and scanning electron
microscopy (SEM, MERLIN VP Compact, Carl Zeiss, Jena, Germany).
The compressibility of each CaCl2 preform was calculated from the
height change extent (E = Dh/h0), where Dh and h0 indicate the
decrease in height and the original height of the investigated pre-
form, respectively. The pore morphologies of Al foams were
observed by an optical microscope. Image-Pro software was used
to analyze the channel size, an important indicator to determine
the pore connectivity of the final foam. The porosities of the repli-
cated foam cylinders were calculated by measuring their mass and
volume determined by the external dimensions.
3. Results and discussion
Fig. 2(a) shows the reconstructed and cross-sectional l-CT mor-
phologies of the CaCl2 preforms obtained by hot-pressing for dif-
ferent holding times. Note that preform A was supported by an
external force provided by a container, while preforms B and C
were self-supporting. This illustrates that after the sintering, stable
connections were formed between the granule contacts from the
initially stacked CaCl2 granules in a shorter time. In this way, the
CaCl2 granules were not disturbed and accordingly not entrapped
Fig. 1. Procedure to prepare high-porosity open-cell aluminum foam.
2
Materials Letters 284 (2021) 129018
by the molten Al during infiltration, which is vital for avoiding
closed pores in the final foam [10]. More significantly, there was
a considerable decrease in the height of the CaCl2 performs and
an increase in the contact area between adjacent granules after
densification by hot-pressing, seen more clearly in Fig. 2(b). Table 1
summarizes the process conditions and structural features of the
CaCl2 preforms and the corresponding Al foams. The value of E
reached 25.5% and 39.4% under holding times of 5 and 30 min,
respectively.
The different stacking densities of the three preforms can be
attributed to the response of the granules to the hot-pressing.
CaCl2 granules of 4.5 mm diameter do not noticeably deform under
the low pressure of 60 kPa (applied in this study) [9]; however,
they are susceptible to cracking under large loads at room temper-
ature owing to their fragile nature and poor plasticity resulting
from the limited sliding systems in them. However, at an elevated
temperature of 700 °C, close to the melting point of anhydrous
CaCl2 (Tm) [11], increased atomic activity and reduced lattice resis-
tance make it easier for dislocations hindered by obstacles to move,
which can improve the plasticity of the CaCl2 granules [12]. Addi-
tionally, CaCl2 granules show creep during hot-pressing. As the
temperature is raised closer to Tm, the creep rate becomes much
higher [13]. The anhydrous CaCl2 granule (from preform A) in
Fig. 2(c) has a porosity of approximately 40%, as seen in Fig. 2(d).
These massive pores not only reduce the area of anti-
deformation but also accommodate strain, further contributing to
significant distortion in a short time. Many pores disappeared
because of compression, and layered regions marked by arrows
were observed in the deformed granule (from preform B) in
Fig. 2(e), as illustrated in Fig. 2(f). Because these CaCl2 granules
are easily deformed by hot-pressing, they become significantly
more compact. This difference would be inherited by Al foams
made from these preforms.
Fig. 3 shows the cross-sectional morphologies of the finally
obtained Al foams. The pores originating from the CaCl2 granules
were interconnected by channels introduced by the contact sur-
faces between the granules. Sample A displayed poor pore connec-
tivity and some closed pores, whereas samples B and C displayed
large channels. During the leaching process, the outermost CaCl2
granules were easily dissolved away first by water. However, the
removal of inside CaCl2 granules require the entrance of water
T. Wan, Y. Liu, C. Zhou et al. Materials Letters 284 (2021) 129018

Fig. 2. (a) Micro-computed tomography morphologies and (b) micrographs of the CaCl2 preforms. (c) Optical and (d) SEM images of an undeformed CaCl2 granule in preform
A and (e) optical and (f) SEM images of a deformed CaCl2 granule in preform B.

Table 1
Summary of the process conditions and structural features of the CaCl2 preforms and the Al foams.

Sample No. Hot-pressing conditions Holding time (min) Height change extent E (%) Channel size (mm) Porosity (%)
A 700 °C+60 kPa 0 0 0.7 ± 0.2 62.3 ± 0.4
B 5 25.5 ± 0.3 1.8 ± 0.3 75.1 ± 0.5
C 30 39.4 ± 0.5 2.4 ± 0.5 83.1 ± 1.2

Fig. 3. Optical images of the final Al foam made from (a) preform A, (b) preform B, (c) preform C.

through the channels. The larger the channel size, the easier for
water to enter inside, making the dissolution and removal process
more smoothly. The foam porosity increased monotonically from
62.3% for 0 min to 83.1% for 30 min, and the channel size grew
monotonically from 0.7 to 2.4 mm respectively (see Table 1). The
porosities of the three samples were in accordance with the stack-
ing densities of the preforms that were approximately character-
ized by E. Because these space-holders continuously deform
without damage and are agglutinated as a whole due to hot-
pressing, they present two primary advantages: First, a densely
packed preform and high-porosity Al foam can be realized, and
second, sufficient granule–granule contact and increased channel
size for CaCl2 removal can be maintained. The fast deformation
and sintering of porous CaCl2 granules within an hour realized by
hot pressing make this space-holder technique an effective one
for adjusting the porosity and channel size of foams.

3
T. Wan, Y. Liu, C. Zhou et al.
4. Conclusions
In summary, we prepared open-cell Al foams with high-
porosity via the high-temperature deformation of porous CaCl2
granules as space-holders in the space-holder technique. The pack-
ing densities of the CaCl2 preforms and hence the porosities of Al
foams could be varied by adjusting the holding time under hot-
pressing. Al foam with porosity over 80% can be obtained by this
method, and the leaching of space-holders is made easier by
increasing the channel size.
CRediT authorship contribution statement
Tan Wan: Conceptualization, Methodology, Software, Investiga-
tion, Visualization, Writing - original draft. Yuan Liu: Conceptual-
ization, Writing - review & editing, Supervision, Data curation.
Canxu Zhou: Investigation, Formal analysis, Writing - review &
editing. Xiang Ding: Writing - review & editing, Data curation.
Xiang Chen: Validation, Formal analysis, Visualization. Yanxiang
Li: Investigation, Supervision, Data curation.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Materials Letters 284 (2021) 129018
Acknowledgement
The present research was supported by the National Science
Foundation of China (No. 51771101).
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